Complexes of 2-heptadecylimidazolines



2,789,115 COMPLEXES F Z-I-IEPTADECYLINIIDAZGLDIES John N; Hogsett, Charleston, W. Va, assignor to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application November 4, 1955, Serial No. 545,103

7 Claims. (Cl. 26ll299) This invention relates to complexes of Z-he ta-decylimidazolines and .to a process for their preparation. More particularly, this invention relates to chelates of Z-heptadecylimidazolines, as new compositions of matter and to a process for their preparation.

I have discovered that novel chelates of Z-heptadecylimidazolines are formed by reacting a metallic compound with a 2-heptadecylimidazoline An embodiment of the present invention is a class of new compositions of matter which are chelates formed by reacting a metallic salt With a 2-heptadecylimidazoline. A specific chelate, which is illustrative of this embodiment of my invention is tri(heptadecylimidazoline acetic acid) iron III sulfate (C132H2G4024N12S3Fe2) Which can be represented by the structural formula:

These compositions include the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline silver nitrate and diheptadecylimidazoline copper sulfate.

My compositions also include chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: di(heptadecylirnidazoline acetic acid) sodium sulfate, di(heptadecylimidazoline acetic acid) sodium hypophosphate, di(heptadecylimidazoline acetic acid) silver nitrate, di(heptadecylimidazoline acetic acid) copper sulfate.

The chelates of my invention can also be formed by reacting Z-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline zinc nitrate, diheptadecylimidazoline zinc chloride, diheptadecylimidazoline cadmium sulfate, diheptadecylimidazoline cadmium nitrate, diheptadecylimidazoline mercury sulfate and diheptadecylimidazoline mercury bromide.

My chelates also include those formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic acid) magnesium sulfate, di(heptadecylimidazoline acetic acid) magnesium chloride, di(heptadecylimidazoline acetic acid) States Patent G "ice Zinc chloride, di(heptadecylimidazoline acetic acid) cadmium sulfate, di(heptadecylimidazoline acetic acid) cadmium nitrate, di(heptadecylimidazoline acetic acid) mercury sulfate and di(heptadecylimidazoline acetic acid) mercury bromide.

The compositions of my invention also include the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group III of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline aluminum sulfate, triheptadecylimidazoline aluminum nitrate and triheptadecylimidazoline aluminum chloride.

My compositions also include chelates formed by reacting acid salts of Z-heptadecylimidazoline with the salts of the metals of group IH of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) aluminum sulfate, tri(heptadecylimidazoline acetic acid) aluminum nitrate and tri(heptadecylimidazoline acetic acid) aluminum chloride.

The compositions of my invention also include the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group IV of the periodic table. Illustrative of such chelates is diheptadecylimidazoline lead nitrate.

Still other compositions Within the scope of my invention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline With the salts of the metals of group .IV of the periodic table. Illustrative of such chelates is di(heptadecylimidazoline acetic acid) lead nitrate.

Other compositions Within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group VI of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline chromium sulfate, triheptadecylimidazoline chromium nitrate and tniheptadecylimidazoline chromium chloride.

Still other compositions of my invention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group VI of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) chromium sulfate, tri(heptadecylimidazoline acetic acid) chromium nitrate and tri- (heptadecylimidazoline acetic acid) chromium chloride.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group VII of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline manganese nitrate, diheptadecylimidazoline manganese chloride and diheptadecylimidazoline manganese sulfate.

The compositions of my invention also include chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of groupVII of the periodic table. Illustrative of such chelates are: di(heptadecylirnidazoline acetic acid) manganese nitrate, di(heptadecylimidazoline acetic acid) manganese chloride and di(heptadecylimidazoline acetic acid) manganese sulfate.

Another group of compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of gi oup VIII of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline iron sulfate, triheptadecylimidazoline iron phosphate, triheptadecylimidazoline iron nitrate, triheptadecylimidazoline cobalt sulfate and dihep Patented Apr. 16, 1951 r 3 phosphate, tri(heptadecylimidazoline acetic acid) iron nitrate, tri-heptadecylimidazoline acetic acid) cobalt sulfate and di(heptadecylimidazoline acetic acid) nickel nitrate.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri- (heptadecylimidazoline) cerium acid sulfate.

Still other compositions within the scope of my invention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazoline acetic acid) cerium acid sulfate.

, The compounds of the present invention can be prepared by a process which comprises bringing a 2-heptadecylimidazoline into reactive admixture with a metal salt under conditions to produce a chelate.

The metal Salts which are best suited for use in this invention are water-soluble. For this reason, the reaction should be conducted in a solvent-medium which comprises at least 80- percent water. Qther solvents which can be used together with water are methanol, ethanol, isopropanol and pyridine. The two reactants, namely the 2-heptadecylimidazoline and the metal salt, need not be added to the solvent in any particular order. Preferably, however, in the case of 2-heptadecylimidazoline, the metal salt is dissolved in water and the 2-heptadecylimidazoline is dissolved in an alcohol, such as isopropanol, and the two solutions are combined. In the case of Z-heptadecylimidazoline acetic acid, both reactants are preferably dissolved in water.

The reaction is preferably conducted at 20 to 30 C. but can be conducted at temperatures between about C. and about 80 C. 7

The following example is illustrative:

EXAMPLE 1 Tri(heptadecylimidazoline acetic acid) iron III sulfate (C132Hzs4Oz4N12S3Fe2) was prepared as follows:

Two grams of ferric sulfate hydrate (Fe2(SO4)3-7H2O) were dissolved in 3000 cc. of water. To this solution was added 100 ml. of an isopropanol solution containing 29 grams of dissolved acetic acid salt to Z-heptadecylimidazoline. An immediate precipitate formed, which was filtered at 300 mm. Hg in a large Buchner funnel. The precipitate was washed twice with water and vacuumdried at 50 C. and 5 mm. Hg for over 24 hours. The dried precipitate was a light tan powder. The calculated percentage composition for a 100 percent pure compound and the actual compositions found for the iron III chelate prepared as described are compared in Table I. In Table I R is Z-heptadecylimidazoline and MX is metal salt.

Table I PERCENTAGE COMPOSITION OF TRI(HEPTADECYLIMID- AZOLINE AGETIC ACID) IRON III SULFATE These data agree satisfactorily with the theoretical structure of the iron chelate containing 3 moles of 2-heptadecylimidazoline acetic acid per mole of Fe in accordance with the accepted coordin'ant number of 6 for Fe+++ and 6 moles of 2-heptadecylimidazoline acetic acid for the chelate as ferric sulfate FC2(R)6(S04)3.

The other chelates of this invention can be prepared in a similar manner.

The chelates of my invention are useful as fungicides. Representative chelates contemplated herein were tested for fungicidal activity by means of the Slide Germination Test. Essentially this test method consisted of germinating spores in continual contact, on glass slides, with given concentrations of the chemical under test. The germination was observed after 24 hours and the amount of the chemical needed to inhibit germination of 50% (L. D. 50 value) of the spores Was determined. The procedure used is more fully set forth in a paper entitled The Slide-Germination Method of Evaluating Protectant Fungicides, published in Phytopathology, July 1943, vol. XXXIH, No. 7, pp. 627-632. Two different and typical fungi were used .for this test. The fungi tested were Sclerotinia fructicola (Wint.) Rehm (S. f.) and Alternaria oleracae (A. 0.). The values in Table II represent the parts by weight of the chelate under test, in a million parts by weight of liquid, to prevent the germination of 50% of the spores. The liquid used, which of itself did not inhibit germination of the spores, was Lins solution, which consists of 10 grams of dextrose, 2.46 grams of MgSO4-7HzO and 100 m1. of distilled water. Ten milliliters of this solution were added to each 100 milliliters of spore.

- Table 11 ED 50 in parts per million Compound S. f. A. o

Di(heptadecylimidazo1iue acetic acid) sodium sulfate 31-. 62 1. 25-2. 5 Di(hcptadecylirnidzaoline acetic acid) cadmium chloride .31-. 62 2. 5-5 Tri(heptadecylimidazoline acetic acid) aluminum sulfate .62-1. 25 2 5-5 Tri(heptadecylimidzaoline acetic acid) chroruium nitrate 31-. 62 o-l0 Di(heptadecyiimidazoliue acetic acid) manganese chloride .62-1. 25 2. 5 Tri(heptadccyliinidazoliue acetic acid) ferric sulfate 31-. 62 2. 5-5 Triheptadecylimidazoline iron sulfate". 62-1. 25 5-10 Diheptadecylirnidazoline zinc chloride" 62-1. 25 5-10 I claim:

1. A chelate having the structural formula MR1, wherein R is a member selected from the group consisting of 2-heptadecylimidazoline and acid salts thereof, M is a salt of a metal of group VIH of the periodic table and n is an integer having a value of one half the coordination number of said metal.

2. Tri(heptadecylimidazoline acetic acid) iron III sulfate.

3. Tri(heptadecylimidazoline acetic acid) iron phosphate.

4. Tri(heptadecylimidazoline acetic acid) iron nitrate.

5. Tri(heptadecylimidazoline acetic acid) cobalt sulfate.

6. Di(heptadecylimidazoline acetic acid) nickel nitrate.

, 7. The process which comprises bringing into reactive admixture a 2-heptadecylimidazoline witha metal salt in a solvent medium at a temperature of from 0 to C.

No references cited. 1 

1. A CHELATE HAVING THE STRUCTURAL FORMULA MRN, WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMIDAZOLINE AND ACID SALTS THEREOF, M IS A SALT OF A METAL OF GROUP VIII OF THE PERIODIC TABLE AND N IS AN INTEGER HAVING A VALUE OF ONE HALF THE COORDINATION NUMBER OF SAID METAL. 